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Dicyclohexylcarbodiimide → t-Butyldimethylsilyl 6-O-{3-O-allyloxycarbonyl-6-O-benzyl-2-deoxy-4-O-(1,5-dihydro-3-oxo-3lambda5-3H-2,4,3-benzodioxaphosphepin-3yl)-2-[(R)-3-dodecanoyloxy-tetradecanoylamino]-beta-D-glucopyranosyl}-2-azido-4-O-benzyl-3-O-[(R)-3-benzyloxy-dodecanoyl]-2-deoxy-beta-D-glucopyranoside

HRID 628195
Notes
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Reaction equation

HRID 628195 reaction equation
[CH2:1]([O:8][C@H:9]([CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH3:22])[CH2:10][C:11]([OH:13])=[O:12])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1CCC(N=C=NC2CCCCC2)CC1.[CH2:38]([O:41][C:42]([O:44][C@H:45]1[C@H:50]([O:51][P:52]2(=[O:63])[O:58][CH2:57][C:56]3[CH:59]=[CH:60][CH:61]=[CH:62][C:55]=3[CH2:54][O:53]2)[C@@H:49]([CH2:64][O:65][CH2:66][C:67]2[CH:72]=[CH:71][CH:70]=[CH:69][CH:68]=2)[O:48][C@@H:47]([O:73][CH2:74][C@H:75]2[O:88][C@@H:79]([O:80][Si:81]([C:84]([CH3:87])([CH3:86])[CH3:85])([CH3:83])[CH3:82])[C@H:78]([N:89]=[N+:90]=[N-:91])[C@@H:77](O)[C@@H:76]2[O:93][CH2:94][C:95]2[CH:100]=[CH:99][CH:98]=[CH:97][CH:96]=2)[C@@H:46]1[NH:101][C:102](=[O:130])[CH2:103][C@H:104]([O:116][C:117](=[O:129])[CH2:118][CH2:119][CH2:120][CH2:121][CH2:122][CH2:123][CH2:124][CH2:125][CH2:126][CH2:127][CH3:128])[CH2:105][CH2:106][CH2:107][CH2:108][CH2:109][CH2:110][CH2:111][CH2:112][CH2:113][CH2:114][CH3:115])=[O:43])[CH:39]=[CH2:40]>C(Cl)Cl.CN(C1C=CN=CC=1)C>[CH2:38]([O:41][C:42]([O:44][C@H:45]1[C@H:50]([O:51][P:52]2(=[O:63])[O:58][CH2:57][C:56]3[CH:59]=[CH:60][CH:61]=[CH:62][C:55]=3[CH2:54][O:53]2)[C@@H:49]([CH2:64][O:65][CH2:66][C:67]2[CH:68]=[CH:69][CH:70]=[CH:71][CH:72]=2)[O:48][C@@H:47]([O:73][CH2:74][C@H:75]2[O:88][C@@H:79]([O:80][Si:81]([C:84]([CH3:85])([CH3:87])[CH3:86])([CH3:82])[CH3:83])[C@H:78]([N:89]=[N+:90]=[N-:91])[C@@H:77]([O:12][C:11](=[O:13])[CH2:10][C@H:9]([O:8][CH2:1][C:2]3[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=3)[CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH3:22])[C@@H:76]2[O:93][CH2:94][C:95]2[CH:96]=[CH:97][CH:98]=[CH:99][CH:100]=2)[C@@H:46]1[NH:101][C:102](=[O:130])[CH2:103][C@H:104]([O:116][C:117](=[O:129])[CH2:118][CH2:119][CH2:120][CH2:121][CH2:122][CH2:123][CH2:124][CH2:125][CH2:126][CH2:127][CH3:128])[CH2:105][CH2:106][CH2:107][CH2:108][CH2:109][CH2:110][CH2:111][CH2:112][CH2:113][CH2:114][CH3:115])=[O:43])[CH:39]=[CH2:40]
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 3

HCID 10868DicyclohexylcarbodiimideHCID 16216230t-Butyldimethylsilyl 6-O-{3-O-allyloxycarbonyl-6-O-benzyl-2-deoxy-4-O-(1,5-dihydro-3-oxo-3lambda5-3H-2,4,3-benzodioxaphosphepin-3yl)-2-[(R)-3-dodecanoyloxy-tetradecanoylamino]-beta-D-glucopyranosyl}-2-azido-4-O-benzyl-2-deoxy-beta-D-glucopyranosideHCID 67004404(r)-3-Benzyloxy-dodecanoic acid

Product 1

HCID 87233474
t-Butyldimethylsilyl 6-O-{3-O-allyloxycarbonyl-6-O-benzyl-2-deoxy-4-O-(1,5-dihydro-3-oxo-3lambda5-3H-2,4,3-benzodioxaphosphepin-3yl)-2-[(R)-3-dodecanoyloxy-tetradecanoylamino]-beta-D-glucopyranosyl}-2-azido-4-O-benzyl-3-O-[(R)-3-benzyloxy-dodecanoyl]-2-deoxy-beta-D-glucopyranoside
Yield 91%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent2×

Procedure

A solution of (R)-3-benzyloxy-dodecanoic acid 14 (86 mg, 0.281 mmol) and DCC (78 mg, 0.376 mmol) in DCM (5 mL) was stirred at room temperature for 10 min, and then disaccharide 21 (250 mg, 0.188 mmol) in DCM (2 mL) and DMAP (11 mg, 0.094 mmol) were added. The reaction mixture was stirred for another 14 h, after which the solids were removed by filtration, and the residue was washed with DCM (2×1 mL). The combined filtrates were concentrated in vacuo, and the residue was purified by silica gel column chromatography (hexane/ethyl acetate, 4/1, v/v) to give 36 as a white solid (277 mg, 91%). Rf=0.41 (hexane/ethyl acetate, 2/1, v/v). [α]26D=−3.0° (c=1.0, CHCl3). 1H NMR (600 MHz, CDCl3): δ 7.34-7.15 (m, 19H, aromatic), 6.01 (d, 1H, JNH′,2=7.2 Hz, NH′), 5.92-6.86 (m, 1H, OCH2CH═CH2), 5.46 (t, 1H, J2′,3′=J3′,4′=9.6 Hz, H-3′), 5.34 (d, 1H, J=16.8 Hz, OCH2CH═CH2), 5.22 (d, 1H, J=10.8 Hz, OCH2CH═CH2), 5.08-4.97 (m, 7H, H-1′, H-3, H-3L, C6H4(CH2O)2P), 4.61-4.45 (m, 10H, H-1, H-4′, 3×CH2Ph, OCH2CH═CH2), 3.97 (d, 1H, J6′a,6′b=10.5 Hz, H-6′a), 3.88-3.86 (m, 1H, H-3S), 3.81 (d, 1H, J6a,6b=9.5 Hz, H-6a), 3.73-3.68 (m, 3H, H-5′, H-6b, H-6′b), 3.56-3.46 (m, 3H, H-2′, H-4, H-5), 3.28 (dd, 1H, J1,2=7.8 Hz, J2,3=10.2 Hz, H-2), 2.56 (dd, 1H, J2Sa,2Sb=15.6 Hz, J2Sa,3S=7.2 Hz, H-2Sa), 2.44 (dd, 1H, J2Sa,2Sb=15.6 Hz, J2Sb,S3=6.0 Hz, H-2Sb), 2.36 (dd, 1H, J2La,2Lb=15.0 Hz, J2La,3 L=6.0 Hz, H-2La), 2.30-2.21 (m, 3H, H-2L′, H-2L′b), 1.57-1.53 (m, 6H, H-4L, H-4S, H-3L′), 1.24 (broad, 48H, 24×CH2, lipid), 0.90 (s, 9H, SiC(CH3)3), 0.89-0.85 (m, 9H, 3×CH3, lipid), 0.13 (s, 6H, Si(CH3)2). 13C NMR (75 MHz, CDCl3): δ 173.54 (C═O), 170.64 (C═O), 170.03 (C═O), 154.49 (C═O), 138.52-127.43 (aromatic, OCH2CH═CH2), 118.84 (OCH2CH═CH2), 99.34 (C-1′), 97.02 (C-1), 76.00, 75.70, 74.33, 74.08, 73.73, 73.48, 71.46, 71.01, 68.95-67.99 (m), 66.55, −4.13 (Si(CH3)2), −5.32 (Si(CH3)2). HR MS (m/z) calculated for C89H135N4O19PSi [M+Na], 1645.9125. found, 1646.2435.

Workup

  1. customafter which the solids were removed by filtration
  2. washthe residue was washed with DCM (2×1 mL)
  3. concentrationThe combined filtrates were concentrated in vacuo
  4. customthe residue was purified by silica gel column chromatography (hexane/ethyl acetate, 4/1

Sources & evidence

ORD record
ord-ca21e0a3ae64460a82af848b7d7c58ea
Source dataset
uspto-grants-2016_04
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US09309276B2

Reaction notes

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